Mercurated 3-nitro 4-alkyl phenols



Patented Dec. 20, 1938 Walter G. .Christiansen, Glen Ridge, N. J., and Eugene Moness, New York,"N."Y., assignors to E. R. Squibb & Sons, New York, N. Y., a corporation of New York Application December 6, 1934, Serial No.: 756,276

I No Drawing.

6 Claims.

is'invention' relates to, and has for its obct theprovision of, certain mercurated S-nitro 4+"alkyl phenols, and'an' advantageous method of pr ps-rm; them. I r

v Thef' mercurated "3 nitrow 4-alkyl phenols of this invention are comprised by the general formula -iairhereinX -re'presents ---mercury linked .to an responding unmercurated 3 nitro anion; Y represents hydrogen, or mercury linked tofiananion; Z 'represents hydroxy; or X and Z together represent anhydro-mercuri, that is and R represents an alkyl. 1

They may be prepared by interacting the cor 4 alkyl phenols with mercuric acetate, and replacing the acetoxy with the desired anion by means of the compound of that anion with an alkali metal (cf. Whitmores Organic Compounds of Mercury, 1921, DD. 257, 258). Formation of the monomercurated compound is favored by using less of the mercuric acetate in proportion to the unmercurated 3-nitro 4-a1kyl phenol, adding it more slowly, and maintaining a lower reaction temperature. These mercurated 3-nitro 4-alkyl phenols have been found to be active germicides.

EXAMPLES 2,4-dinztro isopropyl benzene 48 g. isopropyl benzene is added dropwise to a stirred solution of 112 cc. concentrated nitric acid in 240 cc. concentrated sulfuric acid, the mixture being continuously cooled externally by means of running cold Water, and the addition being at such a rate as to maintain the temperature at 30-35. On completion of the addition, in aboutan hour, the mixture is heated on the steam-bath for forty-five minutes and cooled, the acid is drawn off, and the separated oil is washed twice with water and dissolved in ether, and the ether solution is washed successively with water, a ten percent solution of sodium carbonate, and water, dried over anhydrous sodium sulfate, and filtered. After distilling off the ether, the crude 2,4-dinitro isopropyl benzene is distilled in vacuo,

coming over as a pale yellow oil at -135/2-3 2-nz'tro 4-aminois pmm/l en I 42' g; 2,4-dinitro isopropyl'benzene is dissolved .in 120 cc. absolute alcohol and a solution of ammonium sulfide (made, by mixing 144 cc. 28% "ammonium hydroxide with 144 cc. absolute alcofhol, isaturating. half the solution with hydrogen .sulfide, and mixing with-the other half) is added, andthe'mixture is boiled gently on a hot plate .for forty-five minutes. The clear dark-red liquid .'is filtered hotfrom separated sulfur, and diluted ,with water.; On 'cooling, orangecrystals form. "These are" filtered oif; washed anddissolved in cc; boiling concentrated hydrochloric-acid.

. The solution is diluted witha liter'of water and "filt ered while hotto remove a slight insoluble 1 residue. On pooling, the crystals of Z-nitro 4-a'mino isopropyl benzene hydrochloride separate out as a light-yellow feathery mass, which on being filtered ofi, dissolved in water, and made slightly alkaline with dilute sodium hydroxide solution, yields the bright orange 2-nitro 4-amino isopropyl benzene.

3-nitro 4-isopropyl phenol 21 g, 2-nitro 4-amino isopropyl benzene is dissolved in a solution of 27 cc. concentrated hydrochloric acid in 150 cc. water. The solution being cooled to and maintained at 0, a solution of 10 g. sodium nitrite in 30 cc. water is added dropwise with stirring, and the clear yellow solution of the diazonium salt is added dropwise to a boiling solution of 30 cc. concentrated sulfuric acid in 250 cc. water. Nitrogen is evolved, and the tarry oil that separates out is extracted with ether. The extract is Washed with water and dried over anhydrous sodium sulfate. The ether being distilled off and the crude tarry oil being distilled in vacuo, there is obtained a darkred viscous oil coming over at 124-140/34 mm. This is dissolved in dilute alkali, the solution is shaken with ether to remove any alkali-insoluble material, and the alkaline solution is separated and acidified with dilute hydrochloric acid. The separated oil is extracted with ether, and the extract is washed free of acid and dried over an- I hydrous sodium sulfate. Distillation of the ether leaves 3-nitro 4-isopropyl phenol.

Di-hydroxymercuri 3-m'tro 4-isopropyl phenol and mono-anhydro-mercuri 3-nitro 4-isopropyl phenol After refluxing for nine hours, the test for divalent mercury being negative, the reaction mixture is cooled, the supernatant liquid is decanted off, and the brown crust formed is washed by decantation with a little methyl alcohol and then with water, and is dissolved in dilute alkali. Saturation with carbon dioxide precipitates dihydroxymercuri 3-nitro 4-isopropyl phenol as a yellowish-brown solid. Filtration and acidificaw tion of the filtrate with dilute acetic acid solution yields a mixture that is about twenty-six percent di-hydroxymercuri 3-nitro ll-isopropyl phenol and seventy-four percent mono-anhydro-mercuri 3- nitro 4-isopropy1 phenol.

Di-hydroxymercuri 3-m'tro 4-methyl phenol and mono-hydromymercu'ri 3-m'tro 4-methyl phenol obtained is filtered off from a slight undissolved residue. Addition of carbon dioxide precipitates a yellowish-brown powder that is about 66% di-hydroxymercuri 3-nitro 4-methyl phenol and 34% mono-hydroxymercuri 3-nitro 4-methyl' phenol, dissolving in dilute alkali to give a clear orange-red solution. 7

Manifestly, by substituting some other alkyl for the isopropyl of the isopropyl benzene in the first exampleas ethyl, normalpropyl, butyl, or

amyland employing the same series of reactions, the corresponding alkyl phenol-as 4-ethyl, 4-normalpropyl, 4-butyl, or 4-amyl, respectivelymay be obtained.

It is to be understood that the foregoing examples are merely illustrative and by no means limitative of the invention, which may be variously otherwise embodied within the scope of the appended claims.

We claim:

1. Di hydroxymercuri 3 nitro 4 isopropyl phenol.

2. Mono-anhydro-mercuri B-nitro 4-isopropyl phenol.

3. Mercurated 3-nitro 4-isopropyl phenol.

4. Mercurated 3-nitro 4-13, phenols, wherein R. represents a lower alkyl having at least three carbon atoms. 7

5. The method of preparing mercurated 3- nitro-4-R phenols, wherein R represents a lower alkyl having at least three carbon atoms, which comprises converting the corresponding alkyl benzene into a 2,4-dinitro alkyl benzene, converting the dinitro compound into a Z-nitro--amino alkyl benzene, replacing the amino group with a hydroxy group, and mercurating the resulting 3-nitro 4-a1kyl phenol 6. The method of preparing mercurated 3- nitro-l-isopropyl phenol, which comprises converting isopropyl benzene into 2,4-dinitro isopropyl benzene, converting'the dinitro compound into 2-nitro-4-amino isopropyl benzene, replacing the amino group with a hydroxy group, and mercurating the resulting 3-nitro ll-isopropyl phenol.

WALTER G. CHRISTIANSEN. EUGENE MONESS. 

